Storage-stable aqueous emulsions of α-silyl terminated polymers

ABSTRACT

Aqueous, storage-stable emulsions of α-silyl terminated polymers are useful as adhesives, sealing compounds and coating materials. The α-silyl terminated polymers correspond to the general formula (I): 
                         
in which R 1  is a linear or branched alkyl or alkoxy group containing 1 to 4 carbon atoms, R 2  and R 3  independently of one another are linear or branched alkyl groups containing 1 to 4 carbon atoms, R 4  and R 6  independently of one another are divalent organic connecting groups, R 5  is a hydrophobic divalent polymer group; and R 7  is a CH 2 SiR 1 (OR 2 )(OR 3 ) group, in which R 1 , R 2  and R 3  have the above meaning or R 7  stands for a group that lends the polymer of the general formula (I) the property of self-emulsification in water by forming an oil in water emulsion.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation under 35 USC Sections 365(c) and 120of International Application No. PCT/EP2006/004372, filed 10 May 2006and published 23 Nov. 2006 as WO 2006/122684, which claims priority fromGerman Application No. 102005023050.4, filed 13 May 2005, each of whichis incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

The present invention relates to aqueous, storage-stable emulsions ofα-silyl terminated polymers, their production and use as adhesives,sealing compounds and coating materials.

DISCUSSION OF THE RELATED ART

Silyl-terminated, moisture curable polymer compounds are increasinglyused as coating materials, sealing compounds and adhesives in theconstruction industry and in the automobile industry. For suchapplications, stringent requirements are placed on the elongation- andadhesion capabilities as well as on the curing rate. In addition, suchsilyl-terminated polymers often possess water repellent properties thatlend excellent water stability and heat stability to the sealingcompounds, coating materials or adhesives prepared from them.

Alkoxy silane terminated polymers are known from the prior art and areutilized as soft elastic sealing compounds, coating materials andadhesives.

Thus, alkoxy silane terminated, moisture curable one-componentpolyurethanes are described in EP-B 0 549 626, which find use, forexample, as caulking compounds. The disclosed compounds exhibit a rapidskin formation and rapidly become tack-free, even after prolongedstorage. However, the disadvantage of the described compounds is thatthey have to be stored in the absence of moisture and over a long periodof storage there exists the danger of irreversible changes inproperties.

In the past, in order to overcome this disadvantage, experiments werecarried out to manufacture emulsions or emulsions of silyl terminatedpolymers.

Aqueous polyurethane dispersions for coatings that comprise alkoxysilanes are described in U.S. Pat. No. 5,919,860 and U.S. Pat. No.5,041,494. Here, the polyurethanes are modified with ionic groups.

However, the described emulsions mostly possess a low solids content. Ifsuch emulsions are used for adhesively bonding absorbent materials, thenthe high water content leads to a high loading of the substrate withwater. For example, in paper adhesion, this can lead to unwanted changesin shape of the substrate.

WO 91/08244 relates, for example, to stone protection agents thatcomprise alkoxy silyl terminated polyurethanes. However, the polymercontents of the described emulsions are very low, and lie between 5 and30 wt. %. The described emulsions are neither useful as surface coatingagents in the context of manufacturing mechanically resilient coatingsnor as sealants or adhesives.

A problem associated with the majority of emulsions of silyl terminatedpolymers known from the prior art is that only low solids contents canbe produced. Such low solids contents are however, beside theabove-described disadvantage of the impact of water on the substrate,associated with a series of disadvantages such as, for example, veryslow adhesion of non-absorbent substrates.

One possibility for overcoming these disadvantages is published in WO00/35981, which provides emulsions of silyl terminated polymers with ahigh solids content.

BRIEF SUMMARY OF THE INVENTION

However, as in the prior art up to now only dispersions or emulsions ofthe comparatively slow reacting γ-silyl terminated polymers aredisclosed, it was an object of the present invention to provide aqueousemulsions of the significantly higher reactive α-silyl terminatedpolymers, which in addition to a high solids content exhibit a storagestability that has not been achieved up to now. The term “solidscontent” is understood in the following as the weight percent fractionof the emulsion components discounting the weight fraction of water inthe emulsion, based on the total weight of the emulsion. This object isachieved by the provision of aqueous, storage stable emulsions of oneα-silyl terminated polymer or a plurality of α-silyl terminated polymersof the general formula (I):

in which R¹ is a linear or branched alkyl or alkoxy group containing 1to 4 carbon atoms, R² and R³ independently of one another are linear orbranched alkyl groups containing 1 to 4 carbon atoms, R⁴ and R⁶independently of one another are divalent organic connecting groups, R⁵is a hydrophobic divalent polymer group; and R⁷ is a CH₂SiR¹(OR²)(OR³)group, in which R¹, R² and R³ have the above meaning or R⁷ stands for agroup that lends the polymer of the general formula (I) the property ofself-emulsification in water by forming an oil in water emulsion; andwherein the emulsion has a pH of 2 to 11 and a solids content of 40 to95 wt. % based on the total weight of the emulsion, and the emulsioncomprises one anionic and/or non-ionic emulsifier or a plurality ofanionic and/or non-ionic emulsifiers that are able to form an oil inwater emulsion; and wherein, for the case where R⁷ stands for a groupthat lends the polymer of the general formula (I) the property ofself-emulsification in water to yield an oil in water emulsion, at leasta part of the emulsifier or the emulsifiers is replaced by polymers offormula (I).

Such emulsions are available by mixing the aqueous fraction of theemulsion with a mixture of the emulsifier(s) and the polymer(s) of thegeneral formula (I).

DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS OF THE INVENTION

In the general formula (I), R¹ preferably stands for methyl, ethyl,methoxy or ethoxy and R² and R³ preferably stand, independently of oneanother, for methyl or ethyl. R¹ particularly preferably stands formethyl or methoxy and R² and R³ for methyl. When an increased reactivityand crosslinkability are desired, then the trimethoxy compounds arepreferred.

R⁴ and R⁶, independently of one another can represent any divalentconnecting groups. The term “divalent”, as used throughout the presentinvention, means that the group in question possesses valences forbonding to the two groups that are directly adjacent to it. For R⁶ forexample, this means that this group possesses a valence for each of thebonds to R⁵ and R⁷. In spite of that, however, the group R⁶ may also bean additionally branched group. This is also the case for the groups R⁴and R⁵.

One of the simplest R⁴ groups results, for example, when an isocyanateterminated α-silane is directly bonded to a hydroxy terminated polymer.In this case the connecting group R⁴ is a urethane group. However,indirect connections of the α-silane with the polymer backbone of thepolymer(s) of formula (I) can also be considered. Thus, the group R⁴ canalso be formed from a connecting molecule that is capable of both acovalent reaction with a functional group of the α-silane and also acovalent reaction with the polymer backbone. Thus, for example,diisocyanates can react with both an amino silane to form a urea groupand with a hydroxy terminated polymer to form a urethane group, wherebya divalent connecting group R⁴ is formed that comprises urea andurethane groups. Similarly, the statement for the connection of theα-silane is also valid for the group R⁷.

In the present invention, connecting groups R⁴ and R⁶ that compriseurea- and/or urethane groups, are preferred. However, the connectinggroups R⁴ and R⁶ can comprise any other functional groups or be formedfrom them. Thus, for example, ester groups or amide groups can beinvolved in the connection of the silane and/or the group R⁷ to thepolymer backbone R⁵.

The groups R⁴ and R⁶ particularly preferably stand for a group—NR⁹—(CO)—R¹⁰—, wherein the group R¹⁰ is bonded to R⁵, and R⁹ stands forhydrogen, a linear or branched alkyl group containing 1 to 6 carbonatoms, a cycloalkyl group containing 4 to 6 carbon atoms or an arylgroup containing 5 to 10 carbon atoms; and R¹⁰ stands for a single bondor a group —NR¹¹—R¹²—, wherein the group R¹² is bonded to R⁵, and R¹¹stands for hydrogen, a linear r branched alkyl group containing 1 to 6carbon atoms, a cycloalkyl group containing 4 to 6 carbon atoms or anaryl group containing 5 to 10 carbon atoms; and R¹² stands for a group—R¹³—(NH)_(r)— (CO)— with r=0 or 1, in which R¹³ stands for an alkylarylgroup containing 6 to 11 carbon atoms, an aralkyl group containing 6 to11 carbon atoms, or an aryl group containing 5 to 10 carbon atoms,wherein the CO group is bonded to R⁵.

R⁴ and R⁶ particularly preferably stand independently of one another fora group of formula (II):

wherein the linkage to R⁵ occurs through the urethane group and R¹⁴stands for hydrogen, a linear or branched alkyl group containing 1 to 6carbon atoms, a cycloalkyl group containing 4 to 6 carbon atoms or anaryl group containing 5 to 10 carbon atoms.

The group R⁵ stands for the divalent group of a hydrophobic polymer. Ahydrophobic polymer is understood to mean an essentially water-insolublepolymer. The group R⁵ stands for the divalent group of a polyalkyleneglycol, such as polypropylene glycol, for the divalent group of apolytetrahydrofuran, polyester, polyacrylate, polymethacrylate,polycyanoacrylate, polystyrene, polyamide, polyether polyvinyl acetate,polycaprolactam, polycaprolactone, polybutadiene, polyalkylene such asfor example polyethylene, polyvinyl chloride, polyacrylamide,polyacrylonitrile, polyethylene terephthalate, polycarbonate,polysulfide, polyether ketone, epoxy resin, phenol formaldehyde resin,polyurethane, polysiloxane or a copolymer of monomers of the citedpolymers, such as for example for the divalent group of anethylene/α-olefin copolymer, styrene/butadiene copolymer,styrene/acrylonitrile copolymer, and/or ethylene/vinyl acetatecopolymer. Copolymers are understood to mean copolymers of anystructural type of at least 2 different monomers, on which are based theabove polymers, such as block copolymers, statistical copolymers orgradient copolymers. Different polymer fragments, such as the individualblocks in block copolymers can be linked in this way through divalentorganic connecting groups. The groups defined above as R⁴ and R⁶ areinter alia suitable as divalent organic connecting groups. Minor amountsof hydrophilic monomers, oligomers or polymers can also be polymerizedinto the group R⁵, in so far as the overall hydrophobic property of thepolymer based on R⁵ is retained.

The molecular weight range of the underlying polymer can vary widely andis essentially unlimited. It mainly depends on the processability of thepolymer. The processing of highly viscous polymers can, for example alsobe made accessible by the addition of suitable solvents.

The production of these types of polymers is commonly used by the personskilled in the art and is described, for example in DE 199 58 525 A1.These polymers are usually linked with the silyl group or the group R⁷through the connecting groups R⁴ and R⁶ using reactive α,ω-end groups ofthe polymer. When, for example, the polymer has OH groups or NH₂ groupsin the α,ω-position, then it can react, for example, with an NCO,halide, oxirane, acid anhydride or acid halide group of the silane orthat of the molecule based on the group R⁷ or with corresponding groupsof the connecting molecules based on the connecting elements R⁴ and R⁶.

R⁵ is preferably a divalent polyalkylene glycol group, particularly apolypropylene glycol group, a polyester group or a polytetrahydrofurangroup. The polyester and polytetrahydrofuran groups are particularlypreferred if the adhesive bonds produced by the emulsions are alsointended to have high tensile shear strengths on non-porous substrates.With respect to long-term stability, the polyalkylene glycol-basedpolymers of formula (I) are preferred.

The inventive emulsion comprises anionic and/or non-ionic emulsifiers.The emulsifiers used must be suitable for the production of oil in wateremulsions. According to Römpp Chemie Lexikon (9^(th) extended and newlycompiled edition, Georg Thieme Verlag Stuttgart, vol. 3 (1995), pages1812-1813), these are essentially those emulsifiers with ahydrophilic-lipophilic balance (HLB value) of 8 to 18. The HLB value isunderstood to be a measure of the water- or oil-solubility ofsurfactants. The HLB value of a surfactant mixture or emulsifier mixturecan be calculated from the summed values of its components Comprehensivelists of HLB values of commercially available emulsifiers can be found,for example in Fiedler, Lexikon der Hilfsstoffe for Pharmazie, Kosmetikoder angrenzende Gebiete or in Kirk-Othmer (3) 8, 910-918. In thepresent invention, emulsifiers are preferred with an HLB value of 8 to15.

Exemplary anionic emulsifiers are alkyl sulfates, particularly thosewith a chain length of about 8 to about 18 carbon atoms, alkyl andalkaryl ether sulfates containing about 8 to 18 carbon atoms in thehydrophobic group and 1 to about 40 ethylene oxide (EO) or propyleneoxide (PO) units, or their mixtures, in the hydrophilic part of themolecule, sulfonates, particularly alkyl sulfonates containing about 8to 18 carbon atoms, taurides, esters and half esters of sulfosuccinicacid with monohydric alcohols or alkylphenols containing 4 to about 15carbon atoms, which can be optionally ethoxylated with 1 to about 40 EOunits, alkali metal and ammonium salts of carboxylic acids, for exampleof fatty acids or resin acids containing about 8 to about 32 carbonatoms or their mixtures, partial esters of phosphoric acid and theiralkali metal and ammonium salts. However, alkyl and alkaryl phosphatescontaining about 8 to about 22 carbon atoms in the organic group, alkylether- or alkaryl ether phosphates containing about 8 to about 22 carbonatoms in the alkyl or alkaryl group and 1 to about 40 EO units can beemployed as the anionic emulsifiers. The alkali metal salts of the alkylether sulfates are preferred. Particularly preferred anionic emulsifiersare Disponile (Cognis) of the FES series such as for example 32 IS, 993IS, 77 IS and 61 IS. The anionic emulsifiers can be employedindividually or as mixtures of anionic emulsifiers or as mixtures withnon-ionic emulsifiers.

Exemplary non-ionic emulsifiers are polyvinyl alcohol that still has forexample, about 8 to about 20% of acetate units and a polymerizationdegree of about 200 to about 5000, alkyl polyglycol ethers, preferablythose with about 8 to about 40 EO units and alkyl groups containingabout 8 to about 20 carbon atoms, alkylaryl polyglycol ethers,preferably those with about 8 to about 40 EO units and about 8 to about20 carbon atoms in the alkyl or aryl groups, ethylene oxide/propyleneoxide (EO-PO) block copolymers, preferably those with about 8 to about40 EO or PO units, addition products of alkylamines containing alkylgroups of about 8 to 22 carbon atoms with ethylene oxide or propyleneoxide, fatty or resin acids containing about 6 to about 32 carbon atoms,alkyl polyglycosides containing linear or branched, saturated orunsaturated alkyl groups with on average about 8 to about 24 carbonatoms and an oligo glycoside group with about 1 to about 10 hexose- orpentose units in the agent or mixtures of two or more thereof, naturalproducts and their derivatives such as lecithin, lanolin, sarcosine,cellulose, cellulose alkyl ethers and carboxyalkyl celluloses, the alkylgroups of which each possess 1 to about 4 carbon atoms, linearorgano(poly)siloxanes that comprise polar groups, particularly thosewith alkoxy groups containing up to about 24 carbon atoms and up toabout 40 EO- or PO groups. Alkoxylated, particularly ethoxylated fattyalcohols are the particularly preferred non-ionic emulsifiers. Thenon-ionic emulsifiers can be employed singly or as mixtures of non-ionicemulsifiers or as mixtures with anionic emulsifiers.

In a preferred embodiment of the present invention, the followingemulsifiers are employed: the alkali metal salts, particularly theNa-salt of the C_(12/14)-fatty alcohol ether sulfates, alkylphenol ethersulfates, particularly their alkali metal or NH₄ salts, Na n-dodecylsulfate, di-K oleic acid sulfonate (C₁₈), Na n-alkyl (C₁₀-C₁₃)-benzenesulfonate, Na 2-ethylhexyl sulfate, NH₄ lauryl sulfate (C_(8/14)), Nalauryl sulfate (C_(12/14)), Na lauryl sulfate (C_(12/16)), Na laurylsulfate (C_(12/18)), Na cetylstearyl sulfate (C_(16/18)), Na oleylcetylsulfate (C_(16/18)), nonylphenol ethoxylate, octylphenol ethoxylate,C_(12/14) fatty alcohol ethoxylates, oleylcetyl ethoxylates,C_(16/18)-fatty alcohol ethoxylates, cetylstearyl ethoxylates,ethoxylated triglycerides, sorbitan monolaurate, sorbitan monooleate,sorbitan-20EO-monooleate, Sorbitan-20EO-monostearate, sulfosuccinic acidmonoester di-Na salt, fatty alcohol sulfosuccinates di-Na salt,dialkylsulfosuccinate Na salt or di-Na sulfosuccinamate or mixtures oftwo or more thereof. Likewise, mixtures of anionic and non-ionicsurfactants, mixed non-ionic surfactants, alkylaryl ether phosphates andtheir acid esters, dihydroxystearic acid NH₄ salt, iso-eicosanol, arylpolyglycol ethers, glycerine monostearate can be employed. Particularlypreferred non-ionic emulsifiers are Disponile (Cognis) from the A seriese.g. 3065 and 4065.

The use of non-ionic emulsifiers or a mixture of one anionic emulsifieror a plurality of anionic emulsifiers with one non-ionic emulsifier or aplurality of non-ionic emulsifiers is quite particularly preferred.

Among the non-ionic emulsifiers, a particularly preferred group can berepresented by the general formula (III)

in which R¹ is a linear or branched alkyl group or alkoxy groupcontaining 1 to 4 carbon atoms, R² and R³ independently of one anotherare a linear or branched alkyl group containing 1 to 4 carbon atoms, R⁶is a divalent organic connecting group; and R⁷ stands for a group thatlends the compound of the general formula (III) the property of actingas an oil in water emulsifier in water.

R⁷ preferably stands for a group, which derives from a compound that hasan HLB value of 8 to 18, preferably 8 to 15. R⁷ particularly preferablystands for a [propylene oxy]_(n)[ethylene oxy]_(m)-R⁵ group, wherein n,m and R⁸ are selected such that the HLB value of the corresponding amineH₂N-[propylene oxy]_(n)[ethylene oxy]_(m)-R⁸ ranges from 8 to 15, and R⁸is an aliphatic group, a hydroxyl group or an amino group. A suitableamine of the formula H₂N-[propylene oxy][ethylene oxy]_(m)-R⁸ for theproduction of the emulsifier of the general formula (III) is, forexample Jeffamine® M2070 (Huntsman; n=10, m=31, R⁸=methyl) with an HLBvalue of 13.

As these emulsifiers can be built into the curing network by partial orcomplete hydrolysis of the alkoxy groups during the curing reaction ofthe adhesive, sealant and coating agent, they can be designated asreactive emulsifiers. The use of reactive emulsifiers is preferred,particularly when using polyester- and polytetrahydrofuran-basedpolymers of formula (I), although other systems may be used.

The emulsifier content of the inventive emulsions is preferably lessthan 25 wt. %, more preferably less than 20 wt. %, particularlypreferably less than 15 wt. %, based on the total weight of theemulsion.

In a preferred embodiment of the invention, the emulsifier fraction ofthe emulsion can be zero for the case where the added polymer of thegeneral formula (I) concerns a polymer, in which the group R⁷ stands fora group that lends the polymer of the general formula (I) the propertyof forming an oil in water emulsion in water.

R⁷ in formula (I) preferably stands for a group, which derives from acompound that has an HLB value of 8 to 18, preferably 8 to 15. R⁷ informula (I) particularly preferably stands for a -[propyleneoxy]_(n)[ethylene oxy]_(m)-R⁸ group, wherein n, m and R⁸ are selectedsuch that the HLB value of the corresponding amine H₂N-[propyleneoxy]_(n)[ethylene oxy]_(m)-R⁵ has a value of 8 to 15, and R⁸ is analiphatic group, a hydroxyl group or an amino group. In general,emulsions that comprise a polymer with such a group R⁷ exhibitself-emulsifying properties and mostly do not require additional anionicand/or non-ionic emulsifiers.

Consequently, the present invention also provides α-silyl terminatedpolymers of the general formula (I):

in which R¹ is a linear or branched alkyl group or alkoxy groupcontaining 1 to 4 carbon atoms, R² and R³ independently of one anotherare a linear or branched alkyl group containing 1 to 4 carbon atoms, R⁴and R⁶ independently of one another are a divalent organic connectinggroup, R⁵ is a hydrophobic divalent polymer backbone; and R⁷ stands fora group that lends the polymer of the general formula (I) the propertyof self-emulsification in water by forming an oil in water emulsion.

R⁷ in formula (I) preferably stands for a group, which derives from acompound that has an HLB value of 8 to 18, preferably 8 to 15. R⁷ informula (I) particularly preferably stands for a -[propyleneoxy][ethylene oxy]_(m)-R⁵ group, wherein n, m and R⁸ are selected suchthat the HLB value of the corresponding amine H₂N-[propyleneoxy]_(n)[ethylene oxy]_(m)-R⁸ has a value of 8 to 15, and R⁸ is analiphatic group, a hydroxyl group or an amino group.

In a particularly preferred embodiment of the invention, an emulsiontogether with the polymer of the general formula (I) that is comprisedtherein is provided, wherein R¹ stands for methyl, ethyl, methoxy orethoxy, and R² and R³ independently of one another stand for methyl orethyl, R⁴ and R⁶ independently of one another stand for a divalentconnecting group comprising a urea and/or urethane group, R⁵ is adivalent polytetrahydrofuran or polyester group and R⁷ stands for a-[propylene oxy]_(n)[ethylene oxy]_(m)-R⁵ group, wherein n, m and R⁸ areselected such that the hydrophilic-lipophilic balance value of thecorresponding amine H₂N-[propylene oxy]_(n)[ethylene oxy]_(m)-R⁸ has avalue of 8 to 15, and R⁸ is an aliphatic group, a hydroxyl group or anamino group.

The inventive emulsion has a pH of 2 to 11. Preferably, in order not todamage the substrate, the pH is adjusted to 3 to 10, preferably 4 to 9and more preferably from 4 to 6 in the weak acid region. In particular,for the production of storage stable, self-emulsifying polymers and/orsystems comprising reactive emulsifiers, a pH of 4 to 7, even better 4to 6 has proven to be advantageous. The pH can be stabilized, forexample, by the use of conventional buffer substances and be adjustedwith organic or inorganic acids and bases.

In addition to the obligatory compounds of the general formula (I) andthe non-ionic and/or anionic emulsifiers, the inventive emulsions cancomprise one component as an additive or a plurality of components asadditives, which can also optionally contribute to the solids content of40 to 95 wt. %, preferably 50 to 95 wt. %, particularly preferably 70 to95 or 80 to 95 wt. %. These include, for example, fillers, pigments,protective colloids, pH adjustors such as for example organic andinorganic acids and bases, buffer substances, adhesion promoters such asfor example low molecular weight silanes, tackifiers, catalysts, filmbuilders, plasticizers, redox stabilizers, UV stabilizers or viscositymodifiers. As the compositions of the cited additives can be extremelydifferent, usually those are selected that will not impair the stabilityof the inventive emulsions and which are as inert as possible in regardto the obligatory components of the emulsion.

Accordingly, the inventive emulsion can comprise up to 70 wt. %, forexample about 30 wt. % fillers. Examples of suitable fillers areinorganic compounds that are inert to silanes such as titanium dioxide,chalk, lime powder, precipitated silica, pyrogenic silica, zeolites,bentonites, ground minerals, glass beads, powdered glass, glass fibersas well as further inorganic fillers known to the person skilled in theart, as well as organic fillers, particularly short fibers or hollowplastic beads. Optionally, fillers can be added that lend thixotropy tothe preparation, for example swellable plastics like PVC.

In a particular embodiment, surface-modified fillers can also beemployed.

Generally, all organic and inorganic pigments may be used as pigments,in so far as they do not destabilize the emulsion by interacting withthe components of the emulsion. For example, finely divided silica(Aerosil brand silicas, such as R202, Aeroxide brand silicas, such asT05 or Sipernat brand silicas, such as S22) can be used.

Polyvinyl alcohols (such as Mowiol brand polyvinyl alcohols, e.g. 5-88or 4-88), methyl cellulose and methyl cellulose derivatives (such asCulminal brand methyl cellulose and methyl cellulose derivatives) orpolyvinyl pyrrolidones and copolymers thereof with vinyl acetate (suchas Luviskol brand polymers, e.g. VA64) can be employed, for example asthe protective colloids.

Fundamentally, all inorganic and organic acids and bases, which do notdisadvantageously influence the inventive emulsion, are suitable pHadjustors. Sodium hydrogen carbonate or sodium hydroxide, for example,are suitable for adjusting to basic pH (pH>7), adjustment to acidic pH(pH<7) is carried out, for example, with hydrochloric acid. Theinventive emulsion comprises the pH adjustor, where necessary, in anamount of up to about 10 wt. %, for example about 1 to about 5 wt. % orabout 0.01 to about 1 wt. %, based on the total emulsion.

Moreover, typical buffer systems, such as for example phosphate bufferor citrate buffer systems can be employed.

Suitable exemplary adhesion promoters are low molecular weight silaneswith a molecular weight of less than 200 and which possess one or moresilane groups.

The inventive preparation can comprise up to about 50 wt. % ofconventional tackifiers. Exemplary tackifiers are resins, terpeneoligomers, cumarone-/indene resins, aliphatic, petrochemical resins andmodified phenolic resins. In the context of the present invention,hydrocarbon resins, for example are suitable, such as those obtained bypolymerizing terpenes, principally pinenes, dipentene or limonene.Generally, these monomers are cationically polymerized by initiationwith Friedel-Crafts catalysts. Copolymers of terpenes and othermonomers, for example styrene, isoprene and the like, are also countedamong the terpene resins. The cited resins are used, for example, astackifiers for pressure-sensitive adhesives and coating materials. Theterpene-phenol resins, which are manufactured by acid catalyzed additionof phenols to terpenes or colophonium are also suitable. Terpene-phenolresins are soluble in most organic solvents and oils and are misciblewith other resins, waxes and rubber. In the context of the presentinvention, the colophonium resins and their derivatives, for exampletheir esters or alcohols, are likewise suitable in the above sense asadditives. Further examples may be found in WO 93/23490.

In addition, the inventive preparation can comprise up to about 10 wt. %of catalysts for controlling the curing rate. Suitable exemplarycatalysts are organometallic compounds such as iron or tin compounds,especially the 1,3-dicarbonyl compounds of iron or of 2- or 4-valenttin, in particular the Sn(II) carboxylates or the dialkylSn(IV)dicarboxylates or the corresponding dialkoxylates such as e.g.dibutyltin dilaurate, dibutyltin diacetate, dioctyltin diacetate,dibutyltin maleate, tin(II) octoate, tin(II) phenolate or theacetylacetonates of 2- or 4-valent tin.

Examples of suitable plasticizers are esters such as abietic acidesters, adipic acid esters, azelaic acid esters, benzoic acid esters,butyric acid esters, acetic acid esters, esters of higher fatty acidscontaining about 8 to about 44 carbon atoms, esters of fatty acids withOH groups or epoxidized fatty acids, fatty acid esters and fats,glycolic acid esters, phosphoric acid esters, phthalic acid esters, oflinear or branched alcohols with 1 to 12 carbon atoms, propionic acidesters, sebacic acid esters, sulfonic acid esters, thiobutyric acidesters, trimellitic acid esters, citric acid esters as well as estersbased on nitrocellulose and polyvinyl acetate, as well as mixtures oftwo or more thereof. The asymmetric esters of difunctional, aliphaticdicarboxylic acids are particularly suitable, for example the esterifiedproduct of the monooctyl ester of adipic acid monooctyl ester with2-ethylhexanol (EDENOL DOA, Henkel, Duesseldorf). Pure or mixed ethersof monofunctional, linear or branched C₄₋₁₆ alcohols or mixtures of twoor more different ethers of such alcohols, for example dioctyl ether(available as CETIOL OE, Henkel, Duesseldorf) are also suitable asplasticizers. Furthermore, polyethylene glycols or diurethanes withblocked end groups can also be used.

In addition, the inventive preparation can comprise up to about 10 wt.%, particularly up to about 1 wt. % redox stabilizers or antioxidants.

The inventive preparation can comprise up to about 5 wt. %, for exampleabout 1 wt. % of UV stabilizers. The hindered amine light stabilizers(HALS) are particularly suited as UV stabilizers. In the scope of thepresent invention, the inventive preparation possibly comprises a UVstabilizer that has a silane group and becomes attached to the endproduct during crosslinking or curing. The products LOWILITE 75 andLOWILITE 77 (Great Lakes, USA) are particularly suitable for this.

The present invention also makes available a process for the manufactureof the inventive emulsions, wherein firstly a mixture of one polymer ora plurality of polymers of the general formula (I) is manufactured

in which R¹ is a linear or branched alkyl group or alkoxy groupcontaining 1 to 4 carbon atoms, R² and R³ independently of one anotherare a linear or branched alkyl group containing 1 to 4 carbon atoms, R⁴and R⁶ independently of one another are a divalent organic connectinggroup, R⁵ is a hydrophobic divalent polymer backbone; and R⁷ is aCH₂SiR¹ (OR²)(OR³), in which R¹, R² and R³ have the above meaning or R⁷stands for a group that lends the polymer of the general formula (I) theproperty of self-emulsification in water by forming an oil in wateremulsion; with one anioinic and/or non-ionic emulsifier or a pluralityof anionic and/or non-ionic emulsifiers, which are capable of forming anoil in water emulsion; and wherein, for the case that R⁷ stands for agroup that lends the polymer of the general formula (I) the property ofself-emulsification in water by forming an oil in water emulsion, atleast a part of the emulsifier(s) is replaced by polymers of formula(I).

In a further step, the components of the aqueous emulsion are added tothis mixture, wherein a pH is adjusted to 2 to 11, preferably 3 to 10,more preferably 4 to 9 and even more preferably 4 to 6 or 7 and a solidscontent is adjusted to 40 to 95 wt. %, based on the total weight of theemulsion. In this way there results a storage stable oil in wateremulsion.

Additional non-aqueous components can be added during the mixing of thepolymer(s) with the emulsifier or mixture of emulsifiers. It is criticalthat the aqueous components, such as water, buffer or aqueous pHadjustors are added only after the polymer(s) of formula (I) have beenblended with the emulsifier(s).

In the present invention, “storage stability” is understood to mean theproperty of the inventive emulsions to be capable of storage at atemperature of 23° C. for at least one week, preferably at least twoweeks without demixing and that after storage, adhesive bonds can beproduced, which in comparison with an adhesive bond manufactureddirectly after production of the emulsion, exhibit a tensile shearstrength corresponding to at least 20% of the tensile shear strengthwithout storage. However, the inventive emulsions usually showconsiderably longer storage stabilities (no demixing after periods of 4to 6 months) at significantly higher temperatures (40° C.). Usually, thevalue of the tensile shear strength of adhesive bonds that weremanufactured with emulsions that had been stored for some weeks (forexample 2 weeks) is more than 30%, mostly more than 50% of the valueobtained without storing the emulsion.

In a further aspect, the invention makes available the use of theinventive emulsions for manufacturing adhesives, sealants, coatingagents and polymeric compounds or their use as adhesives, sealants,coating agents and polymeric compounds. In particular, the use for thecited purposes of such emulsions that comprise the inventiveself-emulsifying α-silyl terminated polymer and/or the inventivereactive emulsifier, is preferred.

The inventive emulsions are suitable for a wide field of applications inthe domain of surface coatings, adhesives and sealants. The inventiveemulsions are particularly suitable, for example, as contact adhesives,one component adhesives, two component adhesives, structural adhesives,spray adhesives, adhesive sticks, sealants, particularly joint sealingcompounds, and for surface sealing.

Accordingly, the subject of the invention is also the use of theinventive emulsions as adhesives, sealants, surface coating agents,filling compounds or for manufacturing moldings.

For example, the inventive emulsions and the inventive self-emulsifyingα-silyl terminated polymers are suitable as an adhesive for plastics,metals, mirrors, glass, ceramics, mineral foundations, wood, leather,textiles, paper, cardboard and rubber, wherein the materials can each beadhered to themselves or to any other material.

In the context of an embodiment of the invention, the inventiveemulsions are formulated as a spray adhesive, for example. For this, theinventive preparation, together with a suitable propellant, isintroduced into a suitable spray can.

In the context of a further embodiment of the present invention, theinventive emulsions are formulated as an adhesive stick. For this,suitable thickeners are added to the inventive emulsions. Suitableexemplary thickeners are CARBOPOL 672 (BF Goodrich), SOFTISAN Gel(Contensio), AEROSIL (Degussa), SIPERNAT (Degussa), RILANIT HT extra(Henkel), RILANIT spez. micro. (Henkel), CUTINA HR (Henkel), GENUVISCOcarrageen TPH-1 (Hercules), KLUCEL MF (Hercules), MILLITHIX 925(Milliken), RHEOLATE 204 (Rheox), DISORBENE LC (Roquette), DISORBENE M(Roquette), PERMUTEX RM 4409 (Stahl), STOCKOSORB (Stockhausen), FAVORPAC 230 (Stockhausen), T 5066 (Stockhausen), WACKER HDK H2000 (Wacker)and WACKER HDK V 15 (Wacker).

In addition, the inventive emulsions and the inventive self-emulsifyingα-silyl terminated polymers are suitable, for example, as an adhesivefor plastics, metals, mirrors, glass, ceramics, mineral foundations,wood, leather, textiles, paper, cardboard and rubber, wherein thematerials can each be adhered to themselves or to any other material.

For example, the inventive emulsions and the inventive self-emulsifyingα-silyl terminated polymers can also be used as a surface coating agentfor surfaces made of plastic, metal, mirrors, glass, ceramics, minerals,wood, leather, textiles, paper, cardboard and rubber.

The inventive emulsions and the inventive self-emulsifying α-silylterminated polymers are also suitable for manufacturing moldings of anyshape.

An additional field of application for the inventive emulsions and theinventive self-emulsifying α-silyl terminated polymers is the use asplugs, hole fillers or crack fillers.

An additional subject of the invention consists of an adhesive, asurface coating agent or a sealant, produced with an inventive emulsion.

EXAMPLES

Production of Polymer A

1530 g of ACCLAIM polyol 18200 N (polypropylene glycol with an OH numberof 5.5) were freed from water at 60° C. and 0.6 mbar for 30 minutes.Then, nitrogen was admitted and under a nitrogen purge, 0.3 g TINSTAB BL277 (=DBTL, dibutyltin dilaurate) and then 25.28 g GENIOSIL XL 42(isocyanatomethyl dimethoxy (methyl)silane) were added. The mixture wasthen stirred at 80° C. until quantitative reaction. Under the exclusionof air, plastic cartridges were filled with the still hot Polymer A. Themelt viscosity at 80° C. was 4.0 Pa s (cone/plate method, Brookfield CAP2000 Viscometer, cone 6, 50 rpm, 25 sec.).

Production of Polymer B

650.40 g PE (LIOFOL Polyester 218) were freed from water at 60° C. and1.2 mbar for 45 minutes. Then, nitrogen was admitted and under anitrogen purge, 400 g LUPRANAT MCI (diphenylmethane-2,4′-diisocyanatewere added. After 60 minutes the mixture was cooled down to 60° C.345.50 g GENIOSIL XL 973 (N-phenylaminomethyl trimethoxy silane) werethen added. The mixture was then stirred at 80° C. until quantitativereaction. Under the exclusion of air, plastic cartridges were filledwith the still hot Polymer B. The melt viscosity at 80° C. was 4.6 Pa s(cone/plate method, Brookfield CAP 2000 Viscometer, cone 6, 50 rpm, 25sec.).

Production of Polymer C

409.14 g PTHF 650 (polytetrahydrofuran with an OH number of 175,available from BASF) were freed from water at 80° C. and 3 mbar for 60minutes under an argon purge. It was then allowed to cool down to 60° C.under argon. Under an argon purge, 319.07 g LUPRANAT MCI(diphenylmethane-2,4′-diisocyanate) were added. The mixture was heatedto a temperature of 75° C. for 10 minutes. After the exothermic reactionhad subsided, stirring was continued for 110 minutes at 75° C. 275.60 gGENIOSIL XL 973 (N-phenylaminomethyl trimethoxy silane) were then addedat a temperature of 70° C. under argon. The mixture was then stirred at80° C. until quantitative reaction. Polymer C was filled intocartridges. The melt viscosity at 80° C. was 3.4 Pa s (cone/platemethod, Brookfield CAP 2000 Viscometer, cone 6, 50 rpm, 25 sec.).

Production of Polymer D

59.86 g PTHF 650 (polytetrahydrofuran with an OH number of 179,available from BASF) and 24.69 g PEG 600 (Clariant polyethylene glycol600 PU with an OH number of 186) were freed from water at 80° C. and 3mbar for 60 minutes under an argon purge. It was then allowed to cooldown to 58° C. under argon. Under an argon purge, 68.21 g LUPRANAT MCI(diphenylmethane-2,4′-diisocyanate) were added. After the exothermicreaction had subsided, the mixture was heated for 80 minutes at atemperature of 80° C. 50.26 g WACKER SL 449025 (N-phenylaminomethyldimethoxy(methyl)silane) and 4.85 g GENIOSIL XL 973 (N-phenylaminomethyltrimethoxy silane) were then added at a temperature of 60° C. underargon. The mixture was then stirred at 75° C. until quantitativereaction. Tubes were filled with Polymer D under argon.

Production of Polymer E

150 g PE (LIOFOL Polyester 218) and 50 g Jeffamine® M-2070 (methoxypoly(oxyethylene/oxypropylene)-2-propylamine) were freed from water at60° C. and 0.8 mbar for 30 minutes. Then, nitrogen was admitted andunder a nitrogen purge, 98.05 g LUPRANAT MCI(diphenylmethane-2,4′-diisocyanate) were added. After 60 minutes themixture was cooled down to 60° C. 84.69 g GENIOSIL XL 973(N-phenylaminomethyl trimethoxy silane) were then added. The mixture wasthen stirred for 1 hour at 80° C. until quantitative reaction. Coatedaluminum tubes were filled with the still hot Polymer E. The meltviscosity at 80° C. was 2.7 Pa s (cone/plate method, Brookfield CAP 2000Viscometer, cone 6, 50 rpm, 25 sec.).

Production of Polymer F

95.16 g PTHF 650 (polytetrahydrofuran with an OH number of 174,available from BASF) and 30 g Jeffamine® M-2070 (methoxypoly(oxyethylene/oxypropylene)-2-propylamine, available from Huntsman)were freed from water at 80° C. and 3 mbar for 60 minutes under an argonpurge. It was then allowed to cool down to 78° C. under argon. Under anargon purge, 77.57 g LUPRANAT MCI (diphenylmethane-2,4′-diisocyanate)were added. After the exothermic reaction had subsided, the mixture washeated for 110 minutes at a temperature of 80° C. 66.97 g GENIOSIL XL973 (N-phenylaminomethyl trimethoxy silane) were then added at atemperature of 70° C. under argon. Stirring was continued at atemperature of 80° C. until quantitative reaction (ca. 2 hours). Tubeswere filled with Polymer F under argon. The melt viscosity at 80° C. was1.6 Pa s (cone/plate method, Brookfield CAP 2000 Viscometer, cone 6, 50rpm, 25 sec.).

Production of the (Reactive) Emulsifier I

199.81 g Jeffamine® M-2070 (methoxypoly(oxyethylene/oxypropylene)-2-propylamine, 10PO/31 EO, available fromHuntsman,) and 16.26 g GENIOSIL XL 42 (isocyanatomethyldimethoxy(methyl) silane) were weighed under an argon blanket at roomtemperature. The mixture was stirred at a temperature of 80° C. for 240minutes. Tubes were filled with Product I under argon. The meltviscosity at 80° C. was 0.9 Pa s (cone/plate method, Brookfield CAP 2000Viscometer, cone 6, 50 rpm, 25 sec.).

TABLE 1 Polymers of the General Formula (I):

Polymer R¹ R²/R³ R⁴ R⁵ R⁶ R⁷ A Me MeO NH—CO PPG OC—NH CH₂SiMe(OMe)₂ BMeO MeO N(Ph)-CO—NH-oPh-CH₂-pPh-NH—CO PE OC—NH-pPh-CH₂-oPh-NH—CO—NHCH₂Si(OMe)₃ C MeO MeO N(Ph)-CO—NH-oPh-CH₂-pPh-NH—CO PTHFOC—NH-pPh-CH₂-oPh-NH—CO—NH CH₂Si(OMe)₃ D Me/MeO MeON(Ph)-CO—NH-oPh-CH₂-pPh-NH—CO PTHF/PEG OC—NH-pPh-CH₂-oPh-NH—CO—NHCH₂SiMe(OMe)₂ CH₂Si(OMe)₃ E MeO MeO N(Ph)-CO—NH-oPh-CH₂-pPh-NH—CO PEOC—NH-pPh-CH₂-oPh-NH—CO—NH [PO]₆[EO]₂₉Me F MeO MeON(Ph)-CO—NH-oPh-CH₂-pPh-NH—CO PTHF OC—NH-pPh-CH₂-oPh-NH—CO—NH[PO]₆[EO]₂₉Me Me: methyl; MeO: methoxy Ph: Phenyl; oPh: ortho-phenylene;pPh: para-phenylene PPG: polypropylene glycol group; PE: polyestergroup; PTHF: polytetrahydrofuran group; PEG: polyethylene glycol PO:propylene oxy group; EO: ethylene oxy group

General Production Example for the Inventive Emulsions

10 g of the inventive Polymer A, B, C or D were homogenized with theemulsifier(s) (see Table 2 for quantities) and possible additionalnon-aqueous additives (see Table 2 for quantities) by means of aSpeedmixer (DAC 150 FVZ, from Hauschild) for 20 seconds at 2000 rpm. 1 gbuffer, or when no buffer was used, water was added, and stirring wascontinued for a further 20 seconds. The remainder of the buffer and/orthe remaining water was added portion-wise, whereupon stirring wascontinued each time for 20 seconds thus forming a homogeneous cream.

The optionally comprised additives can be added either at the beginningor also subsequently, each according to the type of additive.Accordingly, non-aqueous components can already be incorporated in theemulsifying polymer mixture, prior to the addition of aqueouscomponents, whereas aqueous components are always blended into theinitially prepared emulsifier-polymer system.

In the case of the self-emulsifying Polymers E and F, the procedure isas above but as required no addition of emulsifier is made.

TABLE 2 Emulsifiers Additives [g] or Polymer [g] [g] Water SolidsFormulation sequence Ex. A B C D E F G H I [g] [wt. %] pH (ex. 26, 27*,28*)  1 10 0.5 0.5 4.8 70 5.8 0.02 HCl  2 10 0.5 0.5 2.3 80 5.8 0.02HCl; 0.8 K30  3 10 0.5 0.5 3.2 75 6.0 0.02 HCl; 0.8 K30  4 10 0.5 0.51.0 84 8.3 1.3 buffer A; 0.1 GF91; 0.02 DBTL  5 10 0.5 0.5 1.8 82 5.91.3 buffer A; 3 KRONOS  6 10 0.5 0.5 1.1 84 5.9 1.3 buffer C; 1 KRONOS 7 10 0.5 0.5 1.8 82 5.9 1.3 buffer C; 3 KRONOS  8 10 0.5 0.5 0.0 91 5.91.3 buffer A; 1 KRONOS  9 10 0.5 0.5 0.9 84 6.0 1.3 buffer A 10 10 0.50.5 5.1 67 4.0 0.02 HCl; 0.8 K30 11 10 0.5 0.5 5.6 65 4.0 0.01 HCl; 0.8K30 12 10 0.5 0.5 2.6 74 9.9 0.8 K30; 2 DYNASYLAN 13 10 0.15 0.15 1.3 809.0 1.3 buffer A; 0.1 GF91; 0.02 DBTL 14 10 0.15 0.15 1.3 80 5.8 1.3buffer A; 15 10 0.5 0.5 2.6 79 4.7 0.8 K30 16 10 0.5 0.5 5.1 67 4.0 0.02HCl; 0.8 K30 17 10 0.5 0.5 2.3 80 5.8 0.02 HCl; 0.8 K30 18 10 0.5 0.51.4 79 9.4 0.07 GF91; 1.5 ACUSOL 19 10 0.5 0.5 0.0 83 6.5 2.5 MOWIOL 2010 0.85 0.85 1.3 82 5.8 1.3 buffer C 21 10 0.15 0.15 1.3 80 5.9 1.3buffer C 22 10 0.05 0.05 1.3 80 6.3 1.3 buffer C 23* 10 0.0 0.0 1.3 80nd 1.3 buffer C 24 10 0.5 0.5 5.0 80 6.5 (polymer + emulsifier) + water25* 10 0.5 0.5 5.0 80 7.5 (water + emulsifier) + polymer 26* 10 0.5 0.55.0 80 7.5 (polymer + water) + emulsifier 27 10 2.0 0.0 64 nd 0.7 HPU; 7buffer A 28 10 1.0 5.2 67 6.1 0.6 HPU 29 10 1.0 5.6 65 3.7 0.6 HPU; HCl30 10 1.0 0.0 73 Nd 0.6 HPU; 4.0 buffer A 31 10 0.5 4.4 69 7.4 0.6 HPU32 10 1.0 0.0 56 nd 0.6 HPU; 9.1 buffer A 33 10 0.5 5.8 63 3.5 0.6 HPU;HCl 34 10 1.0 0.0 67 nd 0.6 HPU; 5.6 buffer A 35 10 1.0 0.0 67 nd 0.6HPU; 5.6 buffer A 36 10 7.0 58 9.5 0.6 HPU; NaOH 37 10 7.0 58 7.0 0.6HPU 38 10 0.0 56 6.0 0.6 HPU; 8.5 buffer A 39 10 7.0 58 4.0 0.6 HPU; HCl40 10 0.0 56 4.8 0.6 HPU; 8.5 buffer B 41 10 0.0 61 5.5 6.8 buffer A;HCl 42 10 0.0 65 4.7 5.9 buffer B 43 10 10.6 48 6.3 44 10 8.8 53 7.2 4510 10.0 50 7.0 0.5 HPU 46 10 0.0 52 4.5 0.6 HPU; 10 buffer B 47 10 0.058 5.8 8 buffer A 48 10 0.0 58 4.8 8 buffer B Abbreviations in Table 2:Polymers A, B, C, D, E and F: see Table 1 G: Fatty alcohol containing 30ethylene oxide units (DISPONIL A3065, Cognis); H: Sodium lauryl ethersulfate (DISPONIL FES77, Cognis); I: Adduct ofmethoxy(polyoxyethylene/polyoxypropylene-2-propylamine (Jeffamine ®M2070, Huntsman) with isocyanatomethyl-dimethoxy-methyl-silane (GENIOSILXL42, Wacker); Buffer A: potassium dihydrogen phosphate/disodiumhydrogen phosphate (92:8, 5 wt. % in water); Buffer B: disodium hydrogenphosphate (5 wt. % in water)/citric acid (10 wt. % in water) 2.2:1;Buffer C: potassium dihydrogen phosphate/disodium hydrogen phosphate (1:1.5 wt. % in water); NaOH: sodium hydroxide (8 wt. %); HCl: hydrochloricacid (10 wt. %); KRONOS: Titanium dioxide (KRONOS 1001, Kronos); K30:polyvinyl pyrrolidone (K30, Fluka, 40 wt. %); ACUSOL: polyacrylate(ACUSOL 801 S, Rohm & Haas, 2 wt. %); MOWIOL: polyvinyl alcohol (MOWIOL4-98, Kuraray, 10 wt. %); GF91: N-Aminoethylaminopropyl trimethoxysilane (GF91, Wacker); HPU: polyurethane-polymer (HPU DSX 1514, Cognis,40 wt. %); DBTL: dibutyltin dilaurate (TINSTAB BL277, Akzo); DYNASYLAN:siloxane oligomer (DYNASYLAN HS 2627, Degussa); nd: not determined*comparative Example:

Evaluation of the Emulsions of Examples 1 to 48

Storage Stability

The samples were stored in glass containers equipped with airtight screwcaps in a climatic exposure test cabinet for various periods at 23° C.or 40° C.

After storage the samples were visually inspected in regard to thestability of the emulsion. The emulsion was considered to be storagestable in the absence of visible phase separation and of any significantchanges in the flowability.

The storage times in weeks or months, during which no separation of theemulsion occurred, are shown in Table 3. The cited times are minimumtimes. As some emulsions were first subjected to storage tests shortlybefore filing of the present application, a storage time of, forexample, “1 week” only reveals that the emulsion was stable after 1 weekof storage. Should a disaggregation have occurred after a specific time,then this is shown in Table 3.

In addition, the tensile shear strength of an adhesive bond produced bythe emulsion directly after production of the emulsion and following 1or 2 weeks storage at 25° C. was determined as is described below.

Tensile Shear Strength

The tensile shear strength for determining the ultimate tensile strengthof adhesive bonds was carried out pursuant to DIN 53283 and DIN 53281.

For this two test specimens (25×100 mm) of solid beech were prepared.The surface to be joined (25×100 mm) is coated on one side with the testemulsion and fixed with two clothes pegs. The samples were stored for 7days at room temperature (25° C.). They were then torn apart by means ofa Tensile Test machine from Zwick, model: Universal test machine (typenumber 144501, load force 10 kN), beech test specimens with an overlapof 20 mm in length and 25 mm width, speed 15 mm/min. The resultingtensile shear strength is measured in N/mm².

The ratio of the tensile shear strength of the adhesive bonds, producedafter storage of the emulsion, to the tensile shear strength of theadhesive bonds, produced immediately after production of the emulsion,are given as “% of the initial value” in Table 4. A value of 80% meansthat 80% of the tensile shear strength of the directly used emulsion isachieved by using a stored emulsion.

TABLE 3 Storage stabilities/Minimum storage times Example nr. of theemulsion Minimum storage time at 23° C. >4 months 1-5, 9, 17, 20, 45 >4months 6-8, 18, 24, 27, 30, 34-38 >4 months 10-12, 16, 21, 22, 31, 33,39, 40 >4 months 13-15, 19, 28, 41, 42, 43, 48 >4 months 46 Breakdownafter 2 weeks 25*, 26* (formulation sequence) Breakdown after 1 day 23*(no addition of emulsifier) 3 months 32, 43, 47 2 months 29 1 month 44Minimum storage time at 40° C. >4 months 2, 3 >4 months 1, 4, 5 >4months 27, 45 >4 months 37-39 >4 months 30, 34, 35 >4 months 40-42, 48 1month 32 5 months 33

TABLE 4 Ratios of tensile shear strengths in percent in comparison withadhesive bonds from non-stored emulsions Tensile shear strength ofEmulsion from adhesive bond of stored emulsions example nr. 1 weekstorage 2 weeks storage 27 55.6 66.7 28 nd 27.3 29 nd 75.8 30 58.1 nd 31nd 45.0 32 72.5 nd 33 nd 107.5 34 19.1 nd 36 65.4 63.5 37 57.7 55.8 3851.1 nd 39 85.7 76.8 40 nd 68.9 41 73.5 63.3 42 62.1 60.6 43 nd 70.3 44nd 56.6 45 25.0 25.0 46 88.1 nd 47 96.7 87.0 48 87.5 80.0 nd: notdetermined

1. An aqueous storage stable emulsion of one or more polymers of thegeneral formula (I):

in which R¹ is a linear or branched alkyl group or alkoxy groupcontaining 1 to 4 carbon atoms; R² and R³ independently of one anotherare a linear or branched alkyl group containing 1 to 4 carbon atoms; R⁴and R⁶ independently of one another are divalent organic connectinggroups; R⁵ is a hydrophobic divalent polymer group; and R⁷ is a-[propylene oxy]_(n)[ethylene oxy]_(m)-R⁸ group, wherein n, m and R⁸ areselected such that the hydrophilic-lipophilic balance value of thecorresponding amine H₂N -[propylene oxy]_(n)[ethylene oxy]_(m)-R⁸ rangesfrom 8 to 15, and R⁸ is an aliphatic group, a hydroxyl group or an aminogroup; wherein the emulsion has a pH of 2 to 11 and a solids content of40 to 95 wt. % based on the total weight of the emulsion, and theemulsion comprises one or more anionic and/or non-ionic emulsifiers,which are capable of forming an oil in water emulsion; and wherein atleast a part of the emulsifier(s) are replaced by polymers of formula(I).
 2. An emulsion according to claim 1, wherein the anionic and/ornon-ionic emulsifier(s), or their mixtures have an HLB value of 8 to 18.3. An emulsion according to claim 1, wherein R¹ stands for methyl,ethyl, methoxy or ethoxy and R² and R³, independently of one another,stand for methyl or ethyl.
 4. An emulsion according to claim 1, whereinR⁴ and R⁶, independently of one another, stand for a divalent connectinggroup comprising urea- and/or urethane groups.
 5. An emulsion accordingto claim 1, wherein R⁴ and R⁶ stand for a group —NR⁹—(CO)—R¹⁰—, whereinR¹⁰ is linked to R⁵, and R⁹ stands for hydrogen, a linear or branchedalkyl group containing 1 to 6 carbon atoms, a cycloalkyl groupcontaining 4 to 6 carbon atoms or an aryl group containing 5 to 10carbon atoms; and R¹⁰ stands for a single bond or a group —NR¹¹—R¹²—,wherein the group R¹² is linked to R⁵, and R¹¹ stands for hydrogen, alinear or branched alkyl group containing 1 to 6 carbon atoms, acycloalkyl group containing 4 to 6 carbon atoms or an aryl groupcontaining 5 to 10 carbon atoms; and R¹² stands for a group—R¹³—(NH)_(r)—(CO)— with r=0 or 1, in which R¹³ stands for an alkylarylgroup containing 6 to 11 carbon atoms, an aralkyl group containing 6 to11 carbon atoms, or an aryl group containing 5 to 10 carbon atoms,wherein the CO group is bonded to R⁵.
 6. An emulsion according to claim1, wherein R⁵ stands for a divalent group of a polypropylene glycol,polytetrahydrofuran, polyester, polyacrylate, polymethacrylate,polycyanoacrylate, polystyrene, polyimide, polyvinyl acetate,polycaprolactam, polycaprolactone, polybutadiene, polyethylene,polyvinyl chloride, polyacrylamide, polyacrylonitrile, polyethyleneterephthalate, polycarbonate, polysulfide, polyether ketone, epoxyresin, phenol formaldehyde resin, polyurethane, polysiloxane or acopolymer of monomers of the cited polymers.
 7. An emulsion according toclaim 1, wherein the emulsifier(s) are selected from the groupconsisting of anionic and non-ionic emulsifiers and compounds of formula(III)

wherein R¹ is a linear or branched alkyl group or alkoxy groupcontaining 1 to 4 carbon atoms, R² and R³ independently of one anotherare a linear or branched alkyl group containing 1 to 4 carbon atoms, andR⁶ is a divalent organic connecting group.
 8. An emulsion according toclaim 1, wherein the emulsifier content is less than 25 wt. %, based onthe total weight of the emulsion.
 9. An emulsion according to claim 1,wherein the pH of the emulsion is 3 to
 10. 10. An emulsion according toclaim 1, comprising a mixture of an anionic and a non-ionic emulsifier.11. An emulsion according to claim 1, wherein the hydrophobic divalentpolymer group R⁵ is a polyester group or a polytetrahydrofuran group.12. An emulsion according to claim 1, additionally comprising one ormore components selected from fillers, pigments, protective colloids, pHadjustors, buffer substances, adhesion promoters, tackifiers, catalysts,film builders, plasticizers, redox stabilizers, UV stabilizers orviscosity modifiers.
 13. A method of adhering a material using anadhesive, said method comprising using an emulsion according to claim 1as said adhesive or as a component of said adhesive.
 14. A method ofsealing a material using a sealant, said method comprising using anemulsion according to claim 1 as said sealant or as a component of saidsealant.
 15. A method of coating a surface using a surface coatingagent, said method comprising using an emulsion according to claim 1 assaid surface coating agent or as a component of said surface coatingagent.
 16. An aqueous storage stable emulsion of one or more polymers ofthe general formula (I):

in which R¹ is methyl, ethyl, methoxy or ethoxy; R² and R³ independentlyof one another are; R⁴ and R⁶ independently of one another are adivalent connecting group comprising urea- and/or urethane groups; R⁵ isa divalent polytetrahydrofuran- or polyester group; and R⁷ is-[propylene oxy]_(n)[ethylene oxy]_(m)-R⁸, wherein n, m and R⁸ areselected such that the hydrophilic-lipophilic balance value of thecorresponding amine H₂N-[ propylene oxy]_(n)[ethylene oxy]_(m)-R⁸ rangesfrom 8 to 15, and R⁸ is an aliphatic group, a hydroxyl group or an aminogroup; wherein the emulsion has a pH of 2 to 11 and a solids content of40 to 95 wt. % based on the total weight of the emulsion, and theemulsion comprises one or more anionic and/or non-ionic emulsifiers,which are capable of forming an oil in water emulsion; and wherein atleast a part of the emulsifier(s) are replaced by polymers of formula(I).
 17. An emulsion according to claim 16, wherein R⁴ and R⁶independently of one another stand for a group of formula (II):

wherein the bond to R⁵ occurs through the urethane group and R¹⁴ standsfor hydrogen, a linear or branched alkyl group containing 1 to 6 carbonatoms, a cycloalkyl group containing 4 to 6 carbon atoms or an arylgroup containing 5 to 10 carbon atoms.
 18. An α-silyl terminated polymerof the general formula (I):

in which R¹ is a linear or branched alkyl group or alkoxy groupcontaining 1 to 4 carbon atoms, R² and R³ independently of one anotherare a linear or branched alkyl group containing 1 to 4 carbon atoms, R⁴and R⁶ independently of one another are divalent organic connectinggroups, R⁵ is a hydrophobic divalent polymer backbone; and R⁷ stands fora group that lends the polymer of the general formula (I) the propertyof self-emulsification in water by forming an oil in water emulsion. 19.An α-silyl terminated polymer according to claim 18, wherein R⁷ standsfor a group that derives from a compound that has an HLB value of 8 to18.
 20. An α-silyl terminated polymer according to claim 18, wherein R⁷stands for a group -[propylene oxy]_(n)[ethylene oxy]_(m)-R⁸, wherein n,m and R⁸ are selected such that the HLB value of the corresponding amineH₂N-[propylene oxy]_(n)[ethylene oxy]_(m)-R⁸ ranges from 8 to 15, and R⁸is an aliphatic group, a hydroxyl group or an amino group.
 21. Anα-silyl terminated polyoxyalkylene derivative of the general formula(III):

in which R¹ is a linear or branched alkyl group or alkoxy groupcontaining 1 to 4 carbon atoms, R² and R³ independently of one anotherare a linear or branched alkyl group containing 1 to 4 carbon atoms, R⁶is a divalent organic connecting group; and R⁷ stands for a group thatderives from a -[propylene oxy]_(n)[ethylene oxy]_(m)-R⁸ group, whereinn, m and R⁸ are selected such that the HLB value of the correspondingamine H₂N-[propylene oxy]_(n)[ethylene oxy]_(m)-R⁸ ranges from 8 to 15,and R⁸ is an aliphatic group, a hydroxyl group or an amino group.